Fiber-forming polmers



Patented June 30, 1953 UNITED STATES PATENT OFFICEZ t FIBER-FORMING POLMERS' Earl W. Gluesenkamp and Alfred B. Craig, Dayton, Ohio, assignors, by mesne assignments, to The Chemstrand Corporation, a corporation of Delaware No Drawing.. Application January 26, 1951,

Serial No. 208,089

This invention relates to polymeric compositions having unusual fiber-forming properties. More specifically the invention relates to polymeric acrylonitrile compositions capable of being converted readily into dyeable general pur pose fibers.

It is well-known that polyacrylonitrile, and various copolymers of acrylonitrile and other olefinic monomers, can be spun into synthetic 20 Claims. (Cl. 260-'-85.5) I

the unsaturated haloaoetates, whereby the polymer is treated with tris(dimethylamido)phosphite and then blended with the fiber-forming acrylom'trile resin. Alternatively the unsaturated haloacetate polymer may be first blended with fiber-forming acrylonitrile polymers and subsequently treated with tris(dimethylamido)- phosphite.

The unsaturated haloacetates which are suitfibers having unusual physical properties. Beable'for the practice of this invention may be cause polyacrylonitrile and the many copolymers represented by the generic formula: of acrylonitrile are almost inert chemically, conventional dyeing procedures are not useful in t H I processing them. Many copolymers of acryloni- B-00oH2-X trile have been prepared u i as the 0011101101 wherein R is an alkenyl radical selected from the mers substances which have dye fi group consisting of vinyl, allyl, methallyl and isopolym rs f t is t p ar not l ys satisfactory propenyl, and X is a halogen atom. Suitable ec u of h exoessiyooost 0f the monomeric substances include vinyl chloroacetive comonomers and becaus the introduetionef tate, allyl chloroacetate, methallyl chloroacetate, such substances often .depreciates the desirable isopropenyl chloroacetate, and the corresponding fiber-forming characteristics of the polymer. bromine ana1ogue5 D The p y Purpose Of this invention is to The proportions of the unsaturated halogenprovide a new acrylonitrile polymer composition cgntaining polymer 1 depend upon the degree which has the chemical and physical properties of dye-receptivity desired, and upon the proof poly cr lon i t which is also completeportion r the chloroaoetate in the blending polyy dy p can be m so by simple mer. In general it is desirable to have from two e y p act cable procedures. A further. pur to 20 per cent of the fiber-forming composition Do Of this invention is to provide a means for in the polymeric form of the chloroacetate. converting non-dyeable acrylonitrile polymers Thus, if t blending polymer is 100 per t into a dyec p form A still further P chloroacetate polymer, from two to 24) per cent pose is to provide new general purpose synthetic 111 be required t develop suitable dye recep fibers. tivity. If a copolymer of the chloroacetate and In accordance with this invention it has been another monomer is used, proportionately more found that non-dyeab e fib 1 will be required to obtain the desired end remers of over 80 per cent of acrylonitrileand sult. Copolymers of more than 30 per cent of fram two to 20 per cent of an unsaturatedv ester th haloacetate monomers and up to '70 per cent of an o-haloacetic acid may be rendered of another olefinic monomer may be used. These Oep i e y reaction With tris(dimethy1amid0)- other monomers may be acrylonitrile, methap osphite. The invention is also appl ca to acrylonitrile, vinyl acetat vinyl chloride, vinylthe treatment of any polymers of unsa u '4 idene chloride, styrene, omethylstyrene, and the esters of the a-haloacetic acids. Although the various alkyl acrylates, alkyl methacrylates, alkyl p ym f t un a u at d a-haloaoetates fumarates and the alkyl maleates, wherein the taining less than per cent of aery10 t are alkyl radicals have up to four carbon atoms. Ben usually o g, they are useful when cause copolymers of acrylonitrile have unusual blended in minor proportions with fiber-formi5 solvent and chemical resistance the preferred ing p y f e a 80 D e t' yl blending polymer is one of substantial portions trile. By this blending procedure the non-dytaof acrylonitrile and sufiicient of the chloroacetate able fiber-forming polymers are made capable of monomer to develop dye-receptivity in the porbeing converted into dye-receptive form, if the tions to be blended with the fiber-forming unsaturated haloacetate is present to the extent 50 acrylonitrile' polymers. A very useful blending of two to 20 per cent of the total monomers polymer is'one of 50 per cent of acrylonitrile and present in polymeric form. In the latter modi- 50 per cent of the chloroacetate, for example, fication the method of this invention is appl methailyl ehieleaeetatecable to any polymers of the unsaturated halo- In the preparation of the fiber-forming polyacetates up to and including per cent of 5 mers which are capable of being converted into dye-receptive form by the practice of this invention there are included the copolymers of 80 percent to 98 per cent of acrylonitrile and from two' to per cent of the unsaturated chloroacetate. If desired, minor proportions, for example, up .to 18 per cent of one or more other monomers may be copolymerized with thecritical components, for example, methacrylonitrile,

styrene, vinyl acetate, a-methylstyrene, vinyl- 1.1+;

add sufficient tris (dimethylamido) phosphite to chloride, vinylidene chloride, the alkyl, esters of "convert all of the chloroacetate nuclei to the maleic, fumaric, acrylic and methacrylic acids,

wherein the alkyl group has up to four carbon atoms.

The polymers of the unsaturated esters of a.'

chloroacetic acid are preferably prepared in methylamido)phosphite dissolved in a suitable solvent, for example, N,N-dimethylformamide, butyrolactone, ethylene carbonate, and other conventional polyacrylonitrile solvents. In the practice of this invention the solutions of the polymers are mixed withz trisldimethylamido phosphitef byi; means bf; any f'cojnventional mechanical mixer, for example, Banbury mixer, roll mill or dough mixers. It is generally desirable to phosphonium groups, although this does not aqueous medium in the presence of a water-solev ,H,

uble peroxy catalyst and in the presence of an} agent which maintains the polymer formed in a fine but granular dispersed condition; -Suitable-- peroxy catalysts are the alkali metal persulfates and suitable dispersing agents are the alkali metal salts of sulfonated hydrocarbons. Polymerization may be conducted by batch proce-. dures, by continuous procedures, or by combinations of these procedures. A preferred method of preparation involves a batch procedure wherein the desired monomers are mixed and charged gradually throughout the polymerization. Unusually uniform polymers may be obtained by also charging the catalyst and emulsifier continuously or in increments throughout the course of the reaction. More uniform polymerization conditions may be achieved by operating at uniform temperatures, for example, the reflux temperature of the medium, especially if the operation is so conducted as to provide a constant temperature at reflux. g If desired, the polymerization reaction may be conducted in the presence of a redox agent, for example, sulfur dioxide, sodium bisulfite, thiosulfate, or other sulfur compounds inwhich the sulfur is present in an oxidizable condition. Other optional procedures may involve the use of regulators which serve as chain terminators to prevent the formation of very high molecular weight increments, agents of this type being tertiary-dodecyl mercaptan, thioglycolic acid, and thioglycidol. z

In order to convert the chloroacetate polymers or the fiberforming blends containing increments of the chloroacetate polymers itis necessary to react the chloroacetate group with tris(dimethylamido)phosphite. This a reaction serves to convert the chloroacetate into a phos-r phonium derivative which is reactive with acid dyestuffs. The polymers so treated are then capable of use in the fabrication of general purpose fibers.

The polymer may be treated with the tris(di methylamido phosphite by reaction with the polymer in the finely divided solid state, in solution in a suitable solvent or in the form of the finished fiber. If the polymer is in solid form, obviously only the surface will be reacted chemically, and if the polymer thus treated is subsequently dissolved and spun into fibers, the amount of efiective component on the surface will be diluted when spun into fiber form. Accordingly, the preferred practice involves chemical treatment in solution state, where it is possible to approach stoichiometric reaction, or in the fiber form where saturation of chemical ac-'- tivity may be achieved on the surface.

It has been found that the most readily dyeable fibers are prepared by reaction with the tris(dinecessarily have ,to occur. Obviously, if the extent of reactionis materially less than stoichiometric, it will benecessary to have a larger proportionoftl e.chloroacetate nuclei present than ;is required generally for effective dye acceptance.

In general if the reaction is suificient to convert to' phosphonium groups from two to ten per cent of the monomer present in the copolymers or blended copolymers a satisfactory result will be achieved, andif onlyfrom :two to ten per cent of the monomer is in the form of unsaturated chloroacetate monomer asubstantially complete reaction will be desirable. I

The new blended compositions may be .fabricated into synthetic fibers; by conventional wet or dry spinning procedures.-. After stretching the fibers to develop the necessary orientation and the incident tensile strength, and thereafter shrinking the fibers to improve their thermal resistance, valuable general purpose fibers are ob tained, i Y

; Further details of-this invention are set forth with respectto the ,followingexamples:

A'copolymer of 95. percent of acrylonitrile and fiyepercent of ,r'nethallyl chloroacetatelwas dis solved to the'extent diabqut 20 per cent in N,N dimethylacetamide by intimately mixing the components at 130.85? C. for one hour. The solution was cooled to 60? C. and 15.4 grams of trisdimethylamid0 phosphite was added thereto. The solution was stirred for 310 minutes and then, spun into fibers by extruding it through a spinneret having 30 apcrtures'each'ODOSE; in. in diameter.' The fiber was stretched 150 per cent during washing, dried and thereafter stretched tfil per cent in a steam atmosphere.

A slreinof V fiber was dyed n a bath containing0.02 gram of Wool Fast Scarlet G. Supra dye 9.1 gram of sulfuric acid, and 40 ml. of water'for each gram; of fiber. All of the dye was absorbed from the dyebath in 1 hour at C. and the fiber assumed a vivid scarlet color. v A fiber made of thesame copolymer without treatment with tris (dimethylamido) phosphite was dyedto a very pale pink color under the same conditions in an identical dyebath.

Example 2 'A copolymer of 92 per cent of acrylonitrile and eight per 'cent' of allyl-chloroacetate was dissolvedto the extentof ten per cent in dimethylacetamide. A stoichiometric equivalent (based on the allyl chloroacetate in the solution) of his- (dimethylamido) phosphite was added to the solution and thereafter heated for one hour at 60 C; vAn analysis of-the polymer demonstrated that 80 per cent'of the chlorine had-been convertedrto ionic chlorine present in the phosphonium compound. Films werecastfrom the solutionwhich were capable of exhaustingthe standard dyebathdescribed in thepreceding expernnent. V-

Example 3 A copolymer of 60 per cent by weight of acrylonitrile and 40 per cent of methallyl chloroacetate. was blended with a copolymer of 97 per cent acrylonitrile and 3 per cent vinyl acetate to form a 5 per cent methallyl chloroacetate blend. Sufficient N,N-dimethyl acetamide was added during the blending operation to form a solution of about 18 per cent solids. Fiber was spun in the manner described in Example 1.

A one gram sample of the fiber was treated with an excess of tris(dimethylamido)phosphite for 3 hours at 100 C. After washing the fiber was found to be unusually receptive of dye using the dyebath described in Example 1.

What is claimed is:

1. A method of preparing a dye-receptive polymer which comprises reacting tris(dimethylamido phosphite and a polymer of a monomeric substance of which at least two percent by weight of the total monomer content is a compound of the structure:

7 compound an alkenyl chloroacetate.

3. A method of preparing a dye-receptive polymer which comprises reacting tris(dimethylamido)ph0sphite and a copolymer of 80 to 98 percent by weight of acrylonitrile and from two to 29 percent of a compound of the structure:

RO-COHz-X wherein R is an alkenyl radical selected from the group consisting of vinyl, allyl, methallyl and isopropenyl and X is a halogen atom.

4. The method defined in claim 3 wherein the compound is an alkenyl chloroacetate.

5. A method of preparing a dye-receptive polymer which comprises reacting tris(dimethylamido)phosphite with a blend of a polymer of a monomeric substance of which acrylonitrile is at least 80 percent of the total monomeric content and a blend of a polymer of a monomeric substance of which at least 20 percent is a compound of the structure:

'Ro- LoH2X wherein R. is an alkenyl radical selected from the group consisting of vinyl, allyl, methallyl and isopropenyl, and X is a halogen atom, and up to 80 percent of another polymerizable mono-olefinic monomer.

6. The method as defined in claim'5 wherein the compound is an alkenyl chloroacetate.

'7. A method of preparing a dye-receptive polymer which comprises reacting tris(dimethy1- amido phosphite with a copolymer of polymerizable monomeric substances of which at least 20 percent of the total polymerizable monomers is a compound of the structure:

wherein R is an alkenyl radical selected from the group consisting of Vinyl, allyl, methallyl and isopropenyl, and X is a halogen atom and up to 80 percent of another polymerizable mono-olefinic monomer, and thereafter blending the reacted polymer with a polymer of a polymerizable monomeric substance of which at least 80 percent of the total polymerizable monomer is acrylonitrile.

8. The method defined in claim '7 wherein the compound is an alkenyl chloroacetate.

9.' A dye-receptive polymer which comprises a polymer of a polymerizable monomeric substance of which at least two percent of the total polymerizable monomer is a compound of the struc ture:

- finic monomer, said polymer having been reacted with tris (dimethylamido) phosphite.

10. The dye-receptive polymer defined in claim 9 wherein the compound is an alkenyl chloroacetate.

11. The dye-receptive polymer defined in claim 9 wherein the compound is vinyl chloroacetate.

12. The dye-receptive polymer defined in claim 9 wherein the compound is allyl chloroacetate.

13. The dye-receptive polymer defined in claim 9 wherein the compound is methallyl chloroacetate.

14. The dye-receptive polymer defined in claim 9 wherein the compound is isopropenyl chloroacetate.

15. A dye-receptive polymer which comprises a copolymer of to 98 percent acrylonitrile and from 2 to 20 percent of a compound of the structure:

RO-O-CH2X wherein R is an alkenyl radical selected from the group consisting of vinyl, allyl, methallyl and isopropenyl, and X is a halogen atom, said copolymer having been reacted with tris(dimethylamido) phosphite.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Coover et a1 Apr. 1, 1950 Number 

1. A METHOD OF PREPARING A DYE-RECEPTIVE POLYMER WHICH COMPRISES REACTING TRIS(DIMETHYLAMIDO) PHOSPHITE AND A POLYMER OF A MONOMERIC SUBSTANCE OF WHICH AT LEAST TWO PERCENT BY WEIGHT OF THE TOTAL MONOMER CONTENTS IS A COMPOUND OF THE STRUCTURE:
 5. A METHOD OF PREPARING A DYE-RECEPTIVE POLYMER WHICH COMPRISES REACTING TRIS(DIMETHYLAMIDO) PHOSPHLITE WITH A BLEND OF A POLYMER OF A MONOMERIC SUBSTANCE OF WHICH ACRYLONITRILE IS AT LEAST 80 PERCENT OF THE TOTAL MONOMERIC CONTENT AND A BLEND OF A POLYMER OF A MONOMERIC SUBSTANCE OF WHICH AT LEAST 20 PERCENT IS A COMPOUNF OF THE STRUCTURE: 